Article for cleaning and conditioning fabrics

ABSTRACT

A laundry article utilizing a water-insoluble substrate is disclosed. This article is added to the automatic washer, and is subsequently carried into the dryer with the fabrics in order to provide cleaning, fabric softening and static control benefits. A method for obtaining cleaning and static control benefits, using these articles, is also disclosed.

BACKGROUND OF THE INVENTION

The desirability of providing fabric softening and static controlbenefits to fabrics which are laundered and are then dried in anautomatic clothes dryer is well known. However, since the compositionswhich provide fabric softening and static control benefits are generallyseparate from the detergent composition used to clean the fabrics, theiruse, in order to obtain these benefits, results in some degree ofinconvenience to the person doing the laundry. For example, thedetergent composition must be measured out and added at the start of thewashing cycle, while the fabric softening and static control compositionrequires a separate measuring operation and is usually added to thewashing machine at a different time during the washing cycle. Thus, theuse of most softening/static control compositions requires theinconvenience of additional pouring and measuring operations, as well asthe necessity of having to remain close to the washing machine duringits operation, so that the composition may be added at the proper time.

Various solutions to this problem have been proposed in the art.Detergent compositions, as well as fabric conditioning compositions,have been separately incorporated with water-insoluble substrates foraddition to the washing machine or the automatic dryer during thelaundering process. These compositions have the advantage of eliminatingthe additional pouring and measuring steps generally attendant to theuse of conventional powder and liquid softening and static controlcompositions, thereby reducing the chance of spillage and waste. U.S.Pat. No. 3,694,364, Edwards, issued Sept. 26, 1972, teaches the use ofan amine-coated modified cellulosic substrate which releasably containsa detergent composition. The substrate is added to the wash solution inorder to introduce the detergent composition into the washing system,while the substrate scavenges and adsorbs undesirable dirt and anionicdyes which are present in the laundry solution. However, the use of sucha composition still requires the separate measuring and addition of thefabric conditioning/static control composition at a later time in thelaundering cycle, if such a benefit is desired.

Many patents, such as U.S. Pat. No. 3,442,692, Gaiser, issued May 6,1969; U.S. Pat. No. 3,632,396, Zamora, issued Jan. 4, 1972; U.S. Pat.No. 3,686,025, Morton, issued Aug. 22, 1972; and U.S. Pat. No.3,936,538, Marshall et al, issued Feb. 3, 1976, teach methods ofincorporating various fabric conditioning compositions, such as staticcontrol compositions, on insoluble substrates. When these substrates areadded to an automatic dryer, or to the rinse cycle of an automaticwasher, the fabrics being laundered receive the fabric conditioningbenefit. However, even with these compositions, the detergentcomposition required to clean the fabrics, must be separately measuredout and added to the laundry solution, and the fabric conditioningsubstrate compositions must be added at another time during thelaundering process.

One possible solution to this inconvenience would be to include thefabric conditioning agent in the detergent composition itself. However,additional problems result when various quaternary ammonium compounds,which are known in the art to possess beneficial antistatic properties,are placed in detergent compositions which contain anionic surfactants,which are commonly employed in the laundering of fabrics. The oppositeelectrical charges of the two compounds lead not only to the mutualattraction of the surfactants, which results in the formation ofinsoluble compounds and the depletion of the respective materials, butalso to reversal of the electrical charges upon fabric surfaces exposedto the wash liquid. This reversal results in undesirable effects such asincreased soil redeposition on fabrics and poor soil removal. U.S. Pat.No. 3,936,537, Baskerville, Jr. et al, issued Feb. 3, 1976, disclosesparticulate detergent compositions, having static control particleswithin a specific size range, which permit the incorporation ofquaternary ammonium fabric conditioning compounds into granular orpowder-form detergent compositions, and which yield both cleaning andstatic reduction benefits to fabrics washed therewith. The attainment ofeffective static control benefits using such compositions depends uponthe entrapment of the quaternary ammonium compound-containing particlesin the fabrics during the washing process, which, under certainconditions, may result in the undesirable buildup of such particles inlaundered fabrics or in various parts of the automatic washer and dryer.In addition, a certain amount of these quaternary ammonium-containingparticles will fail to become so entrapped and, thus, their staticcontrol effect will be lost.

It is thus an object of the present invention to provide a substratearticle which efficiently yields fabric conditioning benefits when usedin the laundering process.

It is a further object of the present invention to formulate a laundryarticle which provides both cleaning and fabric conditioning benefits tofabrics laundered with it.

It is also an object of this invention to provide a convenient, easy touse detergent composition, which does not require limitations as toparticle size necessary in order to obtain static control, and whichyields fabric-care benefits in both the automatic washer and theautomatic dryer.

It is a still further object of the present invention to provide amethod for obtaining both cleaning and static control benefits forlaundered fabrics, utilizing a substrate detergent composition.

SUMMARY OF THE INVENTION

According to the present invention there is provided a substrate-formlaundry article, which provides both cleaning and fabric conditioningbenefits, and which is used in both the automatic washer and dryerduring the laundering process, consisting essentially of awater-insoluble substrate, carrying:

(a) an effective amount of a detergent composition comprising from about5 to 95% of a water-soluble surface-active agent; and

(b) an effective amount of an intimate mixture, having a maximumsolubility in water of 50 ppm at 25° C, and a softening point of from100° to 200° F, consisting essentially of

(i) from about 10 to 90% by weight of quaternary ammoniumfabric-conditioning compounds having the formula [R₁ R₂ R₃ R₄ N]⁺ Y⁻,wherein at least one, and not more than two, of the R₁, R₂, R₃, or R₄groups is an organic radical containing a group selected from a C₁₂ toC₂₂ aliphatic radical, or an alkyl phenyl or alkyl benzyl radical having10 to 16 carbon atoms in the alkyl chain, the remaining group or groupsbeing selected from C₁ to C₄ alkyl, C₂ to C₄ hydroxy alkyl, and cyclicstructures in which the nitrogen atom forms part of the ring, Yconstitutes an anionic radical selected from the group consisting ofhydroxide, halide, sulfate, methyl sulfate, and phosphate ions; and

(ii) from about 10 to 90% by weight of a dispersion inhibitor, being asolid organic material having a maximum solubility in water of 50 ppm at25° C and a softening point in the range of 100° to 200° F, saidmaterial being selected from the group consisting of paraffinic waxes,cyclic and acyclic mono- and polyhydric alcohols, substituted andunsubstituted aliphatic carboxylic acids, esters of cyclic and acyclicmono- and polyhydric alcohols and acids, condensates of C₂ to C₄alkylene oxide with any of the foregoing types of materials whether ornot said materials themselves meet the above solubility and softeningpoint limits, and mixtures thereof.

Preferred substrates for use herein include flexible, water-insolublewet-strength paper, woven cloth and nonwoven cloth substrates.

In addition to the substrate, surfactant, quaternary ammonium, anddispersion inhibitor components, the detergent compositions used in thearticles of the present invention may also include other componentsnormally found in detergent compositions. Examples of such componentsinclude: detergency builder salts, fabric softening agents,soil-suspending agents, corrosion inhibitors, dyes, optical brighteners,germicides, fillers, pH adjusting agents, enzymes, and the like.

A method for providing both cleaning and fabric conditioning benefits tolaundered fabrics, utilizing the substrate articles of the presentinvention in both the automatic washer and dryer, is also disclosed.

DETAILED DESCRIPTION OF THE INVENTION

The laundry articles of the present invention comprise a water-insolublesubstrate and an intimate mixture of a quaternary ammonium fabricconditioning compound and a dispersion inhibitor. Fabric conditioningarticles of this type are disclosed in concurrently filed U.S. patentapplication Ser. No. 781,399, Jones, Articles for Conditioning Fabrics,incorporated herein by reference. The articles of the present inventionalso contain a detergent component. Each of these components will bediscussed in detail hereinafter.

Substrates

The substrates employed herein are water-insoluble and are solid orsubstantially solid materials. They can be dense or open in structure,preferably the latter. Examples of suitable materials which can be usedas a substrate herein include, among others, foam, foil, sponge, paper,woven cloth, and nonwoven cloth. Preferred substrates are made from aflexible material and include those made from paper, woven cloth andnonwoven cloth. The term "cloth," as used herein, means a woven ornonwoven fabric or cloth used as a substrate, in order to distinguish itfrom the term "fabric" which means the textile fabric which is desiredto be laundered. Absorbent capacity, thickness, or fiber density are notlimitations on the substrates which can be used herein, as long as thesubstrates exhibit sufficient wet-strength so as to maintain theirstructural integrity through the complete washing and drying cycles inwhich they are used. Further, the substrates must have certain thermalstability characteristics, i.e., they should not have a melting point orignite at temperatures below 300° F, preferably about 425° F, in orderto permit their use in automatic clothes dryers. Preferably, thesubstrates employed herein are wet strength paper or nonwoven cloth.

Paper substrates which can be employed herein encompass the broadspectrum of known paper structures and are not limited to any specificpapermaking fiber or wood pulp. Thus, the fibers derived from softwoods, hard woods, or annual plants (e.g., bagasse, cereal straw, andthe like), and wood pulps, such as bleached or unbleached kraft,sulfite, soda ground wood, or mixtures thereof, can be used. Moreover,the paper substrates which can be employed herein are not limited tospecific types of paper, as long as the paper exhibits the necessarywet-strength and thermal stability.

A specific example of a paper substrate preferred herein is a two-plypaper having a basis weight of about 50 l lbs. per 2,880 sq. ft. madefrom, for example, a mixture of ground wood and kraft-bleached woodpulps. Another example is the absorbent, multi-ply toweling paperparticularly preferred in U.S. Pat. No. 3,686,025, Morton, issued Aug.22, 1972 and disclosed in U.S. Pat. No. 3,414,459, Wells, said patentsbeing incorporated herein by reference.

The preferred nonwoven cloth substrates used in the invention herein cangenerally be defined as adhesively bonded fiberous products, having aweb or corded fiber structure (where the fiber strength is suitable toallow carding) or comprising fiberous mats, in which the fibers aredistributed haphazardly or in a random array (i.e., an array of fibersin a carded web wherein partial orientation of the fibers is frequentlypresent as well as a completely haphazard distributional orientation) orsubstantially aligned. The fibers can be natural (e.g., wool, silk,jute, hemp, cotton, linen, sisal, or ramie) or synthetic (e.g., rayon,cellulose ester, polyvinyl derivatives, polyolefins, polyamides, orpolyesters). Any diameter or denier of the fiber, generally up to about10 denier, can be used in the present invention.

Methods of making nonwoven cloths suitable for use herein are not a partof this invention and, being well known in the art, are not described indetail herein. Generally, such cloths are made by dry- or water-layingprocesses in which the fibers are first cut to desired lengths from longstrands, passed into a water or air stream, and then deposited onto ascreen, through which the fiber-laden air or water is passed. Thedeposited fibers are then adhesively bonded together, dried, cured, andotherwise treated as desired to form the nonwoven cloth. Nonwoven clothsmade of polyesters, polyamides, vinyl resins, and other thermoplasticfibers can be spun bonded, i.e., the fibers are spun out onto a flatsurface and bonded (melted) together by heat or by chemical reactions.

When the substrate component of the fabric conditioning/detergentarticles herein is a nonwoven cloth made from fibers depositedhaphazardly or in a random array on the screen, the compositions exhibitexcellent strength in all directions and are not prone to tear orseparate when used in both the washer and the dryer.

Preferably, the nonwoven cloth is water-laid or dry-laid and is madefrom cellulosic fibers, particularly from regenerated cellulose orrayon, which are lubricated with a standard textile lubricant.Preferably, the fibers are from about 3/16 to about 2 inches in lengthand are from about 1.5 to about 5 denier. It is also preferred that thefibers are at least partially oriented haphazardly, particularlysubstantially haphazardly, and are adhesively bonded together with ahydrophobic or substantially hydrophobic binder resin, particularly witha nonionic self-crosslinking acrylic polymer or polymers. A preferredcloth comprises by weight about 85% fiber and about 15% binder resinpolymer, and has a basis weight of from about 50 to about 90 grams persquare yard.

The substrates which are used in the fabric conditioning detergentarticles herein, can take a variety of forms. For example, the substratecan be in the shape of a pad, ball or puff, or it can be a sheet orswatch of woven or nonwoven cloth. When the substrate is paper ornonwoven, individual sheets of desired length and width can be used, ora continuous roll of desired width from which a measured length is tornoff, may be employed.

The substrates used in the present invention may be formed such thatthey have slit or aperture openings, in order to improve theirfunctioning in the automatic dryer. Such openings are described in U.S.Pat. No. 3,944,694, McQueary, issued Mar. 16, 1976; U.S. Pat. No.3,956,556, McQueary, issued May 11, 1976; U.S. Pat. No. 4,007,300,McQueary, issued Feb. 8, 1977; and U.S. Pat. No. 4,012,540, McQueary,issued Mar. 15, 1977, all of which are incorporated herein by reference.

The substrates usable herein can be "dense," or they can be open andhave a high amount of "free space." Free space, also called "voidvolume," is that space within a substrate structure which is unoccupied.For example, certain absorbent, multi-ply paper structures compriseplies embossed with protuberances, the ends of which are mated andjoined. This paper structure has free space between the unembossedportions of the plies, as well as between the fibers of the paper pliesthemselves. A nonwoven cloth also has such space among its fibers. Thefree space of the substrate can be varied by modifying the density ofthe fibers of the substrate. Substrates with a high amount of free spacegenerally have low fiber density, and substrates having high fiberdensity generally have a low amount of free space.

The amount of free space which a material has is not essential to itsemployment as a substrate herein. However, the amount of free space inthe substrate structure may affect the amount of the surfactant andfabric conditioning components which must be applied to the substrate inorder to achieve a desired coating effect.

The Surfactant

Preferred laundry articles of the present invention additionally containa detergent composition which comprises from about 5 to 95% by weight ofa water-soluble surface-active agent. Any detersive surfactant known inthe art may be used in the articles of the present invention. It ispreferred that the detergent composition carried by the substratearticles of the present invention contain from about 15 to 90% of thesurfactant component, most preferably from about 20 to 85%.

Preferred water-soluble surface-active agents for use in the articles ofthe present invention include those selected from the group consistingof anionic surfactants, nonionic surfactants, zwitterionic surfactantsand mixtures thereof. These water-soluble surfactants include any of thecommon anionic, nonionic, and zwitterionic detersive surfactants wellknown in the detergency arts. The surfactants listed in U.S. Pat. No.3,717,630, Booth, issued Feb. 20, 1973 and U.S. Pat. No. 3,332,880,Kessler et al, issued July 25, 1967, each incorporated by reference, areuseful in the present invention. Nonlimiting examples of surfactantssuitable for use in the instant compositions are as follows:

Water-soluble salts of the higher fatty acids, i.e., "soaps," are usefulas an anionic surfactant herein. This class of surfactants includesordinary alkali metal soaps such as the sodium, potassium, ammonium, andalkanolammonium salts of higher fatty acids containing from about 8 toabout 24 carbon atoms and preferably from about 10 to about 20 carbonatoms. Soaps can be made by direct saponification of fats and oils or bythe neutralization of free fatty acids. Particularly useful are thesodium and potassium salts of the mixtures of fatty acids derived fromcoconut oil and tallow, i.e., sodium or potassium tallow and coconutsoaps.

Another class of anionic surfactant includes water-soluble salts,particularly the alkali metal, ammonium and alkanolammonium salts, oforganic sulfuric reaction products having in their molecular structurean alkyl group containing from about 8 to about 22 carbon atoms and asulfonic acid or sulfuric acid ester group. (Included in the term"alkyl" is the alkyl portion of acyl groups.) Examples of this group ofsynthetic surfactants which can be used in the present detergentcompositions are the sodium and potassium alkyl sulfates, especiallythose obtained by sulfating the higher alcohols (C₈ -C₁₈ carbon atoms)produced by reducing the glycerides of tallow or coconut oil; and sodiumand potassium alkylbenzene sulfonates, in which the alkyl group containsfrom about 9 to about 15 carbon atoms in straight chain or branchedchain configurations, e.g., those of the type described in U.S. Pat.Nos. 2,220,099 and 2,477,383, incorporated herein by reference.

Other anionic surfactant compounds useful herein include the sodiumalkyl glyceryl ether sulfonates, especially those ethers or higheralcohols derived from tallow and coconut oil; sodium coconut oil fattyacid monoglyceride sulfonates and sulfates; and sodium or potassiumsalts of alkyl phenol polyethylene oxide ether sulfate containing about1 to about 10 units of ethylene oxide per molecule and wherein the alkylgroups contain from about 8 to about 12 carbon atoms.

The alkaline earth metal salts of synthetic anionic surfactants areuseful in the present invention. In particular, the magnesium salts oflinear alkylbenzene sulfonates, in which the alkyl group contains from 9to about 15, especially 11 to 13, carbon atoms, are useful.

Other useful anionic surfactants herein include the water-soluble saltsof esters of α-sulfonated fatty acids containing from about 6 to 20carbon atoms in the ester group; water-soluble salts of2-acyloxy-alkane-1-sulfonic acids containing from about 2 to 9 carbonatoms in the acyl group and from about 9 to about 23 carbon atoms in thealkane moiety; alkyl ether sulfates containing from about 10 to 20carbon atoms in the alkyl group and from about 1 to 30 moles of ethyleneoxide; water-soluble salts of olefin sulfonates containing from about 12to 24 carbon atoms; and β-alkyloxy alkane sulfonates containing fromabout 1 to 3 carbon atoms in the alkyl group and from about 8 to 20carbon atoms in the alkane moiety.

Preferred water-soluble anionic organic surfactants for use hereininclude linear chain alkylbenzene sulfonates containing from about 10 to16 carbon atoms in the alkyl group; alkyl sulfates containing from about10 to 20 carbon atoms; the coconut range alkyl glyceryl sulfonates; andalkyl ether sulfates wherein the alkyl moiety contains from about 10 to20 carbon atoms and wherein the average degree of ethoxylation variesbetween about 1 and 6.

Specific preferred anionic surfactants for use herein include: sodiumlinear C₁₀ -C₁₂ alkylbenzene sulfonate; triethanolamine C₁₀ -C₁₂alkylbenzene sulfonate; sodium tallow alkyl sulfate; sodium coconutalkyl glyceryl ether sulfonate; and the sodium salt of a sulfatedcondensation product of C₁₄ -C₁₈ alcohol with from about 1 to about 10moles of ethylene oxide.

It is to be recognized that any of the foregoing anionic surfactants caneither be used separately or in mixtures.

Most commonly, nonionic surfactants are compounds produced by thecondensation of an alkylene oxide, especially ethylene oxide(hydrophilic in nature), with an organic hydrophobic compound, which isusually aliphatic or alkyl aromatic in nature. The length of thehydrophilic polyoxyalkylene moiety which is condensed with anyparticular hydrophobic compound can be readily adjusted to yield awater-soluble compound having the desired degree of balance betweenhydrophilic and hydrophobic properties. Examples of nonionic surfactantssuitable for use herein include:

(1) The polyethylene oxide condensates of alkyl phenols. These compoundsinclude the condensation products of alkyl phenols having an alkyl groupcontaining from about 6 to 12 carbon atoms in either a straight chain orbranched chain configuration with ethylene oxide, said ethylene oxidebeing present in an amount equal to 5 to 25 moles of ethylene oxide permole of alkyl phenol. The alkyl substituent in such compounds can bederived, for example, from polymerized propylene, diisobutylene, and thelike. Examples of compounds of this type include nonyl phenol condensedwith about 9.5 moles of ethylene oxide per mole of nonyl phenol; dodecylphenol condensed with about 12 moles of ethylene oxide per mole ofphenol; dinonyl phenol condensed with about 15 moles of ethylene oxideper mole of phenol; and di-isooctylphenol condensed with about 15 molesof ethylene oxide per mole of phenol. Commercially available nonionicsurfactants of this type include Igepal CO-630 marketed by the GAFCorporation, and Triton X-45, X-114, X-100 and X-102, all marketed bythe Rohm and Haas Company.

(2) The condensation products of aliphatic alcohols with from about 1 toabout 25 moles of ethylene oxide. The alkyl chain of the aliphaticalcohol can be either straight or branched, primary or secondary, andgenerally contains from about 8 to about 22 carbon atoms. Examples ofsuch ethoxylated alcohols include the condensation product of about 6moles of ethylene oxide with 1 mole of tridecanol; myristyl alcoholcondensed with about 10 moles of ethylene oxide per mole of myristylalcohol; the condensation product of ethylene oxide with coconut fattyalcohol wherein the coconut alcohol is a mixture of fatty alcohols withalkyl chains varying from 10 to 14 carbon atoms in length and whereinthe condensate contains about 6 moles of ethylene oxide per mole ofalcohol; and the condensation product of about 9 moles of ethylene oxidewith the above-described coconut alcohol. Examples of commerciallyavailable nonionic surfactants of this type include Tergitol 15-S-9marketed by Union Carbide Corporation, Neodol 23-6.5 marketed by ShellChemical Company and Kyro EOB marketed by the Procter & Gamble Company.

(3) The condensation products of ethylene oxide with a hydrophobic baseformed by the condensation of propylene oxide with propylene glycol. Thehydrophobic portion of these compounds has a molecular weight of fromabout 1500 to 1800 and exhibits water insolubility. The addition ofpolyoxyethylene moieties to this hydrophobic portion tends to increasethe water-solubility of the molecule as a whole, and the liquidcharacter of the product is retained up to the point where thepolyoxyethylene content is about 50% of the total weight of thecondensation product, which corresponds to condensation with up to about40 moles of ethylene oxide. Examples of compounds of this type includecertain of the commercially available Pluronic surfactants marketed byWyandotte Chemicals Corporation.

(4) The condensation products of ethylene oxide with the productresulting from the reaction of propylene oxide and ethylenediamine. Thehydrophobic moiety of these products consists of the reaction product ofethylenediamine and excess propylene oxide, said moiety having amolecular weight of from about 2500 to about 3000. This hydrophobicmoiety is condensed with ethylene oxide to the extent that thecondensation product contains from about 40% to about 80% by weight ofpolyoxyethylene and has a molecular weight of from about 5,000 to about11,000. Examples of this type of nonionic surfactant include certain ofthe commercially available Tetronic compounds marketed by WyandotteChemicals Corporation.

Nonionic surfactants may also be of the semi-polar type includingwater-soluble amine oxides containing one alkyl moiety of from about 10to 28 carbon atoms and two moieties selected from the group consistingof alkyl groups and hydroxyalkyl groups containing from 1 to about 3carbon atoms; water-soluble phosphine oxides containing one alkyl moietyof about 10 to 28 carbon atoms and two moieties selected from the groupconsisting of alkyl groups and hydroxyalkyl groups containing from about1 to 3 carbon atoms; and water-soluble sulfoxides containing one alkylmoiety of from about 10 to 28 carbon atoms and a moiety selected fromthe group consisting of alkyl and hydroxyalkyl moieties of from 1 to 3carbon atoms.

In the detergent compositions used in the instant invention it ispreferred that the particular nonionic surfactants employed have ahydrophilic-lipophilic balance (HLB) of from about 8 to about 15.Preferred nonionic surfactants are the condensation products of alkylphenols, having 6-12 carbon atoms in the alkyl group, with from about 5to 25 moles of ethylene oxide, and the condensation products of C₈ -C₂₂aliphatic alcohols with from about 1 to 15 moles of ethylene oxide, andmixtures thereof. Highly preferred nonionic surfactants are thecondensation products of at least 5 moles of ethylene oxide with a C₁₀-C₁₆ aliphatic alcohol.

Another preferred nonionic surfactant herein comprises a mixture of"surfactant" and "co-surfactant" as described in U.S. patent applicationSer. No. 557,217, Collins, filed Mar. 10, 1975, the disclosure of whichis incorporated herein by reference. The term "nonionic surfactant" asemployed herein encompasses these preferred mixtures of Collins.

Zwitterionic surfactants include derivatives of aliphatic quaternaryammonium, phosphonium, and sulfonium compounds in which the aliphaticmoieties can be straight or branched chain, and wherein one of thealiphatic substituents contains from about 8 to 18 carbon atoms and onecontains an anionic water-solubilizing group. Particularly preferredzwitterionic materials are the ethoxylated ammonium sulfonates andsulfates disclosed in U.S. Pat. No. 3,925,262, Laughlin et al, issuedDecember 9, 1975; U.S. Pat. No. 3,929,678, Laughlin et al, issued Dec.30, 1975; and U.S. patent application Ser. No. 603,837, Laughlin et al,filed Aug. 11, 1975, all of which are incorporated herein by reference.The inclusion of these surfactants in the compositions give excellentclay soil removal performance.

Particularly preferred ethoxylated zwitterionic surfactants are thosehaving the formulae: ##STR1##

Additional preferred zwitterionic surfactants include those having theformula ##STR2## wherein the sum of x + y is equal to about 15.

Quaternary Ammonium Component

The quaternary ammonium fabric softening and antistatic components willnormally be employed in the laundry articles of the present invention inan amount of from about 10 to about 90%, preferably from about 15 toabout 80%, and most preferably from about 20 to 60% by weight of anintimate mixture with the dispersion inhibitor described below.

The compounds useful herein are quaternary ammonium salts of the formula[R₁ R₂ R₃ R₄ N]⁺ Y⁻, wherein R₁ and preferably R₂ represent an organicradical containing a group selected from a C₁₂ to C₂₂ aliphatic radicalor an alkyl phenyl or alkyl benzyl radical having 10 to 16 atoms in thealkyl chain, R₃ and R₄ represent hydrocarbyl groups containing from 1 toabout 4 carbon atoms, or C₂ to C₄ hydroxyalkyl groups and cyclicstructures in which the nitrogen atom forms part of the ring, and Y isan anion such as halide or methylsulfate.

In the context of the above definition, the hydrophobic moiety (i.e. theC₁₂ to C₂₂ aliphatic, C₁₀ to C₁₆ alkyl phenol or alkylbenzyl radical) inthe organic radical R₁ may be directly attached to the quaternarynitrogen atom or may be indirectly attached thereto through an amide,ester, alkoxy, ether, or like grouping.

The quaternary ammonium antistatic components useful herein include bothwater-soluble and substantially water-insoluble materials. For example,the imidazolinium compounds of the structure ##STR3## where R is a C₁₆to C₂₂ alkyl group, possesses appreciable water solubility, but can beutilized in the present invention by mixture with the appropriate leveland type of organic dispersion inhibitor so as to give an ultimatemixture solubility in water of less than 50 ppm at 25° C. Thus,water-soluble quaternary ammonium compounds may be used in thecompositions of the present invention as long as their solubility isadjusted to the proper level by combination with the dispersioninhibitor. Similarly, other relatively water-soluble quaternary ammoniumantistatic agents, such as the diisostearyldimethylammonium chloridesdisclosed in U.S. Pat. No. 3,395,100, Fisher et al, incorporated hereinby reference, may be used in the compositions of the present invention.

However, the preferred quaternary ammonium antistatic components usefulherein are characterized by their limited solubility in water. That isto say, such quaternary salts are essentially insoluble in water,existing therein in what appears to be the mesomorphic liquidcrystalline state.

The quaternary ammonium antistatic agents used in this invention can beprepared in various ways well known in the art and many such materialsare commercially available. The quaternaries are often made from alkylhalide mixtures corresponding to the mixed alkyl chain lengths in fattyacids. For example, the ditallowalkyl quaternaries are made from alkylhalides having mixed C₁₄ -C₁₈ chain lengths. Such mixed di-long chainquaternaries are useful herein and are preferred from a cost standpoint.

Essentially any anionic group can be the counter-ion in the quaternarycompounds useful herein. The anionic groups in the quaternary compoundscan be exchanged, one for another, using standard anion exchange resins.Thus, quaternary ammonium salts having any desired anion are readilyavailable. While the nature of such anions has no effect on thecompositions and processes of this invention, the methyl sulfate andchloride ions are the preferred counter-ions from an availabilitystandpoint; while the methyl sulfate anion is preferred because of itsminimization of corrosive effects on the automatic clothes dryers inwhich it is used.

The following are representative examples of substantiallywater-insoluble quaternary ammonium antistatic agents suitable for usein the articles and processes of the present invention. All thequaternary ammonium compounds listed can be included in the articles ofthe present invention, but the compilation of suitable quaternarycompounds hereinafter is only by way of example and is not intended tobe limiting of such compounds. Dioctadecyldimethylammonium chloride isan especially preferred quaternary antistatic agent for use herein, byvirtue of its high antistatic activity; ditallowalkyldimethylammoniumchloride is equally preferred because of its ready availability and itsgood antistatic activity; other useful di-long chain quaternarycompounds are dicetyldimethylammonium chloride,bis-docosyldimethylammonium chloride, didodecyldimethylammoniumchloride, ditallowalkyldimethylammonium bromide,dioleoyldimethylammonium hydroxide, ditallowalkyldiethylammoniumchloride, ditallowalkyldipropylammonium bromide,ditallowalkyldibutylammonium fluoride, cetyldecylmethylethylammoniumchloride, bis-[ditallowalkyldimethylammonium] sulfate,tris-[ditallowalkyldimethylammonium] phosphate, and the like.Particularly preferred quaternary ammonium antistatic compounds areditallowalkyldimethylammonium chloride and ditallowalkyldimethylammoniummethyl sulfate.

Organic Dispersion Inhibitor

The intimate mixture of the quaternary ammonium compound and thedispersion inhibitor used in the present invention comprises from about10 to about 90%, preferably from about 15 to about 80%, and mostpreferably 25 to about 80% by weight of the organic dispersion inhibitorcomponent. An amount of dispersion inhibitor sufficient to provide aweight ratio of quaternary ammonium compound to dispersion inhibitor offrom about 6:1 to about 1:6, preferably from about 4:1 to 1:4, and mostpreferably from about 3:1 to 1:3, is employed. The intimate mixture ofthe quaternary ammonium softening/antistat and dispersion inhibitorcomponents should have a maximum solubility in water of 50 ppm at 25° C,and a softening point in the range of 100° to 200° F.

The dispersion inhibitor itself should also have a maximum solubility inwater of 50 ppm at 25° C, and a softening point in the range of 100° to200° F, preferably 125° to 200° F, most preferably from 150° to 175° F,and is selected from the group consisting of paraffinic waxes, cyclicand acyclic mono- and polyhydric alcohols, substituted and unsubstitutedaliphatic carboxylic acids, esters of cyclic and acyclic mono- andpolyhydric alcohols and acids, condensates of C₂ to C₄ alkylene oxidewith any of the foregoing types of materials whether or not saidmaterials themselves meet the above solubility and softening pointlimits, and mixtures thereof.

Preferred herein as a dispersion inhibitor, because of its readyavailability, is tallow alcohol, but other useful dispersion inhibitorsinclude other fatty alcohols in the C₁₄ to C₂₆ range, such as myristylalcohol, cetyl alcohol, stearyl alcohol, arachidyl alcohol, behenylalcohol, and mixtures thereof.

Saturated fatty acids having 12 to 24 carbon atoms in the alkyl chainmay also be used as dispersion inhibitors in the present invention.Examples of such compounds include lauric acid, myristic acid, palmiticacid, stearic acid, arachidic acid, and behenic acid, as well asmixtures of these, particularly those derived from naturally occurringsources such as tallow, coconut, and marine oils.

Esters of the aliphatic alcohols and acids are useful dispersioninhibitors, provided they have a total of more than 22 carbon atoms inthe acid and alkyl radicals.

Long chain C₂₂ to C₃₀ paraffinic hydrocarbon materials, such as thesaturated hydrocarbon octacosane having 28 carbon atoms can also beused.

Another preferred class of materials useful in the present invention arethe water-insoluble sorbitan esters which comprise the reaction productof C₁₂ to C₂₆ fatty acyl halides, or fatty acids, and the complexmixtures of cyclic anhydrides of sorbitol collectively known as"sorbitan". The sorbitan esters are complex mixtures of mono-, di-,tri-, and tetraester forms, of which the tri- and tetra- are the leastwater-soluble and hence the most preferred for the purposes of thepresent invention. However, commercially available mixtures of thevarious forms are quite satisfactory provided that the mixture satisfiesthe water-solubility and melting point range constraints for the organicdispersion inhibitor. Typical fatty acids that are suitable for thealkyl portion of the ester are palmitic, stearic, docosanoic, andbehenic acids and mixtures of any of these. These sorbitan esters,particularly the tri- and tetra-esters, provide a degree of fabricsoftening in addition to their function as dispersion inhibitors. Minorproportions of unsaturated C₁₀ to C₂₆ fatty acids present incommercially available fatty acid mixtures, such as coconut-, palm-,tallow-, and marine oil-derived acids are also acceptable. Materials ofthis general class are commercially available under various trade names,such as the Span series sold by Atlas Chemical Corporation. Preferreddispersion inhibitors of this type include the C₁₀ to C₂₂ alkyl sorbitanesters, for example, sorbitan trilaurate, sorbitan trimyristate,sorbitan tripalmitate, sorbitan tristearate, sorbitan tetralaurate,sorbitan tetramyristate, sorbitan tetrapalmitate, sorbitantetrastearate, and mixtures thereof. A particularly preferred dispersioninhibitor of this type is sorbitan monostearate. Another preferred groupof materials are the C₂₀ to C₂₆ mono-, and di-ester forms which alsoprovide fabric softening performance in addition to their function asdispersion inhibitors.

The preferred dispersion inhibitors for use in the articles of thepresent invention include tallow alcohol, sorbitan monostearate andmixtures of them, particularly where the ratio, by weight, of tallowalcohol to sorbitan monostearate is about 1:2. A preferred intimatemixture for use in the articles of the present invention containsditallowalkyldimethylammonium chloride and tallow alcohol in a ratio, byweight, of about 1:1.

The quaternary ammonium antistatic component and the dispersioninhibitor are applied to the substrate articles of the present inventionin the form of an intimate mixture, in an amount effective to yield thedesired fabric softening and static control performance. Preferredarticles of the present invention carry from about 1 to about 20 grams,most preferably from about 2 to 8 grams of the intimate mixture. Thisintimate mixture can be formed by dry mix addition, but a preferredtechnique involves the comelting of the two materials. The comeltingfrequently results in the formation, when the mixture is subsequentlycooled, of a solid phase which is crystallographically distinct fromeither of the individual components. This phase is believed to enhancethe inhibition of the solubility of the quaternary antistat/organicdispersion inhibitor mixture. Other conventional methods of forming anintimate mixture between the quaternary ammonium compound and thedispersion inhibitor may also be used in making the substrate articlesof the present invention. Another method of forming this mixture is byforming a layer of the quaternary ammonium compound on the substrate andcompletely covering it with a layer of the dispersion inhibitor.However, the quaternary ammonium compound may not be placed in a layeron top of the dispersion inhibitor component.

In applying the surfactant and the intimate mixture described above tothe substrate, the components may be either impregnated into or coatedonto the substrate. The term "coating" connotes the adjoining of thesurfactant and intimate mixture components to the surface of thesubstrate. This coating may be done in long continuous strips or insmaller discrete areas on the substrate surface. In a preferredembodiment, the areas of the various components coated onto thesubstrate, particularly the quaternary ammonium/dispersion inhibitormixture, have an average diameter of greater than about 500 microns."Impregnation" is intended to mean the permeation of the entiresubstrate structure, internally as well as externally, with thesurfactant and quaternary/dispersion inhibitor components. Anyconventional methods for coating or impregnating the substrate withthese components may be used in forming the articles of the presentinvention.

A preferred conditioning article, described in concurrently filed U.S.patent application Ser. No. 781,385, Hagner and Wissel, Article forConditioning Fabrics, incorporated herein by reference, can be made byloading the quaternary ammonium/dispersion inhibitor intimate mixtureonto the substrate, such that the mixture penetrates into the substratematerial and extends to a height of from about 1/32 inch to about 1/2inch above the substrate surface. Where the areas of the mixture carriedby the substrate have a height greater than about 1/2 inch, they tend tobreak and chip off from the substrate during the washing and dryingprocess and, hence, lose their softening and static controleffectiveness. It is preferred that the height of the intimate mixturebe from about 1/16 inch to about 3/8 inch, particularly from about 3/32inch to about 1/4 inch, above the substrate.

These preferred articles provide an especially efficient method wherebysoftening and static control benefits may be imparted to launderedfabrics and, therefore, permit the use of lower levels of the quaternaryammonium/dispersion inhibitor mixture. It is preferred that thesesubstrate articles carry from about 0.2 to about 12 grams of theintimate mixture, more preferably from about 0.25 to about 9 grams, mostpreferably from about 1 to about 6 grams, particularly about 2.5 grams.It is also preferred that the intimate mixture cover at least about 1.5square inches, more preferably at least about 3 square inches, and mostparticularly at least about 4 square inches, of the outer substratesurface area. In one embodiment of these preferred articles, aquaternary ammonium conditioning component and tallow alcohol are heatedto about 190°-200° F and are mixed together in a ratio of quat:tallowalcohol of from about 3:1 to 1:3, particularly about 1:1. The mixture isthen placed on the substrate in small spots, such that they penetrateinto the substrate layer, and have a height above the substrate of about3/32 inch.

In a preferred method of making the laundry articles of the presentinvention, the quaternary ammonium/dispersion inhibitor mixture and thesurfactant component are applied to the substrate by a gravure or rotaryscreen printing. The components are applied to the substrate in liquidform. Thus, components which are normally solid at room temperatureshould first be melted or dissolved in a solvent prior to application.In preferred articles, the detergent composition, which includes thesurfactant component, is applied to the substrate in an amount effectiveto provide adequate cleaning of the fabrics to be laundered. Preferredarticles of the present invention carry from about 3 to about 120 grams,particularly from about 20 to about 80 grams, of the detergentcomposition. In another method of application, the components aresprayed onto the substrate as it is unrolled. A further method ofapplication is to separately treat a desired number of individual plies(on one or both sides) of a multi-ply substrate and subsequently joiningthe plies with a known adhesive compound or by sewing or heat-sealingthe plies. This provides a composition which can be untreated on one ofits outer sides, yet contain within it several other plies, each ofwhich is treated on both sides. It is preferred that the quaternaryammonium/dispersion inhibitor mixture be applied to the outer sides ofthe substrate used, in order to facilitate the release of the quaternaryammonium component during the drying process.

In one embodiment of the present invention, a two-layer nonwovensubstrate is used. The detergent composition is loaded between thelayers of the substrate and the outer edges of the substrate are bondedtogether by glue or heat-sealing. The loading of the detergentcomposition on the inside of the substrate article, provides a finishedproduct which is neat and easy to handle for the user. The quaternaryammonium/dispersion inhibitor mixture is loaded on an outer surface ofthe substrate. In this embodiment, the detergent composition may becarried by layers of sponge, foam, paper, woven cloth, or nonwoven clothcontained within the article. Detergent articles having this type ofstructure are described in U.S. patent application Ser. No. 781,378,Flesher and Kingry, filed of even date and incorporated herein byreference. At least one of the substrates used in this embodiment musthave an air permeability of at least about 10 cu. ft. per minute per sq.ft., in order to assure proper release of the detergent composition intothe laundry solution.

In a preferred embodiment of the present invention, the totalcomponents, which are carried by the substrate in the laundry articlesof the present invention, contain from about 1 to 30%, preferably fromabout 3 to 20%, and most preferably from about 4 to 15% of thequaternary ammonium/dispersion inhibitor intimate mixture. It isparticularly preferred that the total components carried by thesubstrate contain from about 0.5 to 7% of the quaternary ammoniumcomponent.

The detergent compositions, which may be included in the articles of thepresent invention, may also, in addition to the surfactant component,contain additional adjunct components which are normally found indetergent compositions. Such additional components are applied to thesubstrate along with the surfactant component, defined above. Forexample, the detergent compositions may include builder salts,especially alkaline, polyvalent anionic builder salts. These alkalinesalts serve to maintain the pH of the cleaning solution in the range offrom about 7 to about 12, preferably from about 8 to about 11, andenable the surfactant component to provide effective cleaning even inthe presence of hardness cations in the laundry solution. It ispreferred that the builder salts are present in an amount of from about1 to 60%, more preferably about 15 to 35%, by weight of the detergentcompositions used in the present invention; although by the properselection of surfactants and other components, effective detergentcompositions, which are free or essentially free of builder salts, maybe formulated for use herein.

Suitable detergent builder salts useful herein can be of the polyvalentinorganic or polyvalent organic types, or mixtures thereof. Nonlimitingexamples of suitable water-soluble, inorganic alkaline detergent buildersalts include alkali metal carbonates, borates, phosphates,polyphosphates, bicarbonates, silicates, and sulfates. Specific examplesof such salts include the sodium and potassium tetraborates, perborates,bicarbonates, carbonates, tirpolyphosphates, orthophosphates,pyrophosphates and hexametaphosphates.

Examples of suitable organic alkaline detergency builder salts are:

(1) water-soluble aminopolyacetates, e.g., sodium and potassiumethylenediamine tetraacetates, nitrilotriacetates, andN-(2-hydroxyethyl) nitrilotriacetates;

(2) water-soluble salts of phytic acid, e.g., sodium and potassiumphytates; and

(3) water-soluble polyphosphonates, including sodium, potassium andlithium salts of ethane-1-hydroxy-1,1-diphosphonic acid; sodium,potassium and lithium salts of methylenediphosphonic acid; and the like.

Additional organic builder salts useful herein include thepolycarboxylate materials described in U.S. Pat. No. 3,364,103,incorporated herein by reference, including the water-soluble alkalisalts of mellitic acid. The water-soluble salts of polycarboxylatepolymers and copolymers, such as are described in U.S. Pat. No.3,308,067, incorporated herein by reference, are also suitable asbuilders. It is to be understood that while the alkali metal salts ofthe foregoing anionic detergents and organic and inorganic polyvalentanionic builder salts are preferred for use herein from an economicstandpoint, the ammonium, and alkanolammonium, e.g., triethanolammonium,diethanolammonium, monoethanolammonium, and the like, water-solublesalts of any of the foregoing detergent and builder anions are alsouseful herein.

A further class of detergency builder materials useful in the presentinvention are insoluble sodium aluminosilicates, particularly thosedescribed in Belgian Pat. No. 814,874, issued Nov. 12, 1974,incorporated herein by reference. This patent discloses and claimsdetergent compositions containing sodium aluminosilicates of the formulaNa_(Z) (AlO₂)_(Z) (SiO₂)_(Y).XH₂ O wherein Z and Y are integers equal toat least 6, the molar ratio of Z to Y is in the range of from 1.0:1 toabout 0.5:1, and X is an integer from about 15 to about 264, saidaluminosilicates having a calcium ion exchange capacity of at least 200mg. eq./gram and a calcium ion exchange rate of at least about 2grains/gallon/minute/gram. A preferred material is Na₁₂(SiO₂.AlO₂)₁₂.27H₂ O.

Mixtures of organic and/or inorganic builders may be used herein. Onesuch mixture of builders is disclosed in Canadian Pat. No. 755,038, andconsists of a ternary mixture of sodium tripolyphosphate, trisodiumnitrilotriacetate and trisodium ethane-1-hydroxy-1,1-diphosphonate.

Other preferred builder materials which may be used in the articles ofthe present invention include alkali metal carboxymethyltartronates,commercially available as about 76% active together with about 7%ditartronate, about 3% diglycolate, about 6% sodium carbonate and about8% water; and anhydrous sodium carboxymethylsuccinate, commerciallyavailable as about 76% active together with about 22.6% water and amixture of other organic materials, such as carbonates.

While any of the foregoing alkaline polyvalent builder materials areuseful herein, sodium tripolyphosphate, sodium nitrilotriacetate, sodiummellitate, sodium citrate, and sodium carbonate are preferred herein foruse as builders. Sodium tripolyphosphate is especially preferred hereinas a builder, both by virtue of its detergency building activity and itsability to suspend illite and kaolinite clay soils and to retard theirredeposition on the fabric surface.

Bleaching agents may also be incorporated in the detergent compositionsused in the present invention. Examples of typical bleaching agents arechlorinated trisodium phosphate and the sodium and potassium salts ofdichloroisocyanuric acid.

The detergent compositions useful in the present invention may alsocontain other adjunct materials commonly used in such compositions.Examples of such components include various soil-suspending agents, suchas carboxymethylcellulose, corrosion inhibitors, dyes, fillers such assodium sulfate and silica, optical brighteners, germicides, pH adjustingagents, enzymes, enzyme stabilizing agents, perfumes, and the like. Inaddition, up to about 5%, preferably from about 0.3% to about 1%, ofTiO₂ may be added to pasty or liquid detergent compositions used in thepresent invention to inhibit bleeding through the substrate layers.

The substrate compositions of the present invention are used in both theautomatic washer and dryer and yield fabric softening and static controlbenefits to the fabrics laundered with them. When the detergentcomposition, including the surfactant component, is included on thesubstrate, the articles of the present invention also provide cleaningbenefits to the fabrics being laundered with it. The substratecomposition is placed in the automatic washing machine together with thefabrics to be laundered, preferably at the start of the washing cycle,and is allowed to remain there until the washing cycle is completed.During this process, the surfactant and adjunct components which arecontained on the substrate are released into the washing solution andprovide a cleaning benefit to the fabrics washed therein, while theintimate mixture is held substantially intact on the substrate. Thefabrics and the same substrate are then tumbled, under heat, in anautomatic dryer until the fabrics are dry. In the course of the dryingprocess, the antistat/dispersion inhibitor mixture, carried on thesubstrate, softens as the fabrics and the substrate approach the dryerair temperature and the tumbling action of the dryer causes this mixtureto deposit onto the fabrics, thus distributing the quaternary ammoniumcomponent over the surface of the fabrics and minimizing the buildup ofstatic charges on them.

All percentages, parts, and ratios herein are by weight unless otherwisespecified.

The following nonlimiting examples illustrate the articles and themethod of the present invention.

EXAMPLE I

A laundry article of the present invention was formed by coating adetergent composition, having the formulation below, on one side of an 8× 103/4 inch sheet of a paper towel, comprising wood pulp, rayon, and alatex binder. An identical sheet of the same type of paper towel wasplaced on top of the coated original sheet, and the edges of the twosheets were sewn together, so as to enclose the detergent compositionbetween the two substrate sheets. The intimate mixture of quaternaryammonium component and dispersion inhibitor, formed by comelting thecomponents, was then applied to the outer surface of the substrate in a3 inch wide strip. Each of the substrate products contained 3.6 grams ofthe intimate mixture on its surface.

A granular detergent composition having essentially the same compositionas that used in the substrate article, was made by spray-drying thecomponents set forth below. The only difference between the granularcomposition and the substrate article was in the amount of watercontained, the granular composition having a smaller amount of water dueto loss in the spray-drying process. The intimate mixture of thequaternary ammonium static control agent and the dispersion inhibitorwas prilled and added to the detergent composition in an amount so as togive a level of 3.6 grams of the mixture per cup usage of the detergentcomposition.

    ______________________________________                                                        Grams added                                                                   per wash load                                                                   Substrate   Granular                                        Component         article     product                                         ______________________________________                                        Detergent Composition:                                                        Sodium C.sub.11.8 linear                                                                        9.2         9.2                                             alkylbenzene sulfonate                                                        Sodium C.sub.14-16 alkyl poly-                                                                  4.6         4.6                                             ethoxylate sulfate                                                            Sodium silicate solids                                                                          9.2         9.2                                             (2.Or)                                                                        Sodium tripolyphosphate                                                                         24.4        24.4                                            Tallow fatty acid 0.4         0.4                                             Water and minors  25.0        15.1                                            Intimate Mixture:                                                             Ditallowalkyldimethyl-                                                                          2.7         2.7                                             ammonium chloride                                                             Tallow alcohol    0.9         0.9                                             ______________________________________                                    

The substrate article and the granular detergent composition were thenused to launder fabrics, under identical conditions, in a Kenmoreautomatic washing machine. For each run a standard 51/2 lb. load ofclothing, containing both synthetic and natural fiber garments, waswashed in a regular agitation cycle, in 100° F wash water which had ahardness of 7 grains of mixed calcium and magnesium per gallon of water.Each load of clothing was then transferred from the washer to a Kenmoreelectric dryer and was dried for 50 minutes. When the substrate articlesof the present invention were used, these articles were transferred fromthe washer to the dryer along with the laundered clothing. The driedclothes were then inserted in a Faraday Cage Voltage Sensing Basket andthe voltage level change was measured as each clothing item was removedfrom the Faraday Cage, yielding the total voltage charge per wash load.The total voltage charge was then divided by the amount of fabricsurface area in each wash load to calculate the voltage per area. Alower voltage per area figure denotes a better static controlperformance by the composition utilized in the washing/drying process.Two laundering and drying runs were made for the substrate article andthe granular detergent composition, and the voltage per square yardresults of these runs were averaged together. The clothing articles thathad been washed in the granular detergent composition had an averagevoltage per square yard value of 2.2, while the clothing articles whichwere laundered using the substrate article of the present invention hadan average voltage per square yard value of 1.4. Since both thesubstrate article and the granular composition contained the same amountof the static control active ingredient per usage, these data indicatethat the use of the substrate article is a more effective and efficientway to deliver the static control benefit than is the granular detergentcomposition. Further, the substrate articles are easier for the user tohandle and provide a method for delivering cleaning and fabricconditioning benefits which necessitate the use of less packagingmaterial and storage space than do conventional compositions.

Substantially similar results are obtained when the anionic surfactantscontained in the article of the present invention are sodium, calcium,or magnesium neutralized anionic surfactants, C₁₀₋₁₆ branched chainalkylbenzene sulfonates, C₁₀₋₁₆ alkyl sulfates, or C₁₀₋₁₆ alkyl ethersulfates.

Comparable results are also obtained when the substrate article containsa nonionic surfactant such as a secondary C₁₁₋₁₅ alcohol condensed with9 moles of ethylene oxide (Tergitol 15-S-9), the condensation product ofC₁₂₋₁₃ alcohol with an average of 5 moles of ethylene oxide, wherein themono- and unethoxylated fractions are stripped away (Neodol 23-3T), orthe condensation product of nonylphenol with 9 moles of ethylene oxide(Igepal CO-630).

Similar results are also obtained when the builder used in the substratearticles is a water-insoluble aluminosilicate builder, e.g., hydratedsodium Zeolite A with an average particle size of 1 to 10 microns,sodium pyrophosphate, sodium carbonate, or sodium 2-oxy-1,1,3-propanetricarboxylate.

Similar results are also obtained where the quaternary ammoniumcomponent used in the substrate article is ditallowalkyldimethylammoniummethyl sulfate, dicetyldimethylammonium chloride,didodecyldimethylammonium chloride, ditallowalkyldimethylammoniumbromide, dioleoyldimethylammonium hydroxide,ditallowalkyldipropylammonium chloride, ditallowalkyldibutylammoniumfluoride, or cetyldecylmethylethylammonium chloride.

Comparable results are also obtained where the dispersion inhibitor usedin the substrate article is replaced by myristyl alcohol, cetyl alcohol,stearyl alcohol, lauric acid, myristic acid, palmitic acid, stearicacid, sorbitan trilaurate, sorbitan trimyristate, sorbitantetrapalmitate, or sorbitan tetrastearate.

EXAMPLE II

A substrate article of the present invention, having the componentformulation below, was formulated in the following manner:

    ______________________________________                                        Component              % by weight                                            ______________________________________                                        Condensation product of                                                                              24.9                                                   C.sub.14-15 alcohol with 7 moles                                              of ethylene oxide per mole                                                    of alcohol (Neodol 45-7)                                                      Triethanolamine        5.8                                                    Magnesium C.sub.11.8 linear                                                                          51.9                                                   alkylbenzene sulfonate                                                        Tallow fatty acid      1.7                                                    Moisture and minors    3.85                                                   Intimate mixture:                                                             Tallow alcohol         5.1                                                    Ditallowalkyldimethyl- 6.75                                                   ammonium chloride                                                             ______________________________________                                    

A single sheet of a commercially marketed paper towel was loaded withthe static control and dispersion inhibitor ingredients by making amixture of the tallow alcohol and the ditallowalkyldimethylammoniumchloride components by comelting them together, and dripping thismixture on the towel in large spots. The ingredients were allowed tocool and solidify on the towel. 4.4 grams of this mixture were loadedonto the towel.

The towel was then dipped into the liquid mixture of the remainingdetergent ingredients and was allowed to soak up 62.5 grams of thecomposition. The wet towel was dried to remove moisture, leaving 32.5grams of the detergent active components on the towel.

This substrate article was added to an automatic washing machine with aload of soiled clothes, and a complete washing cycle of the machine wasrun. The clothes, together with the substrate article, were thantransferred to an electric clothes dryer, which was run until theclothing articles were dry. The substrate article acted to clean thefabrics, and imparted a fabric softening and a static control benefit tothem.

EXAMPLE III

A substrate article, for use in both the washer and the dryer, havingthe composition defined below, is made as as follows:

    ______________________________________                                        Component              % by weight                                            ______________________________________                                        Neodol 45-7            25.4                                                   Triethanolamine        5.9                                                    Magnesium C.sub.11.8 linear                                                                          53.0                                                   alkylbenzene sulfonate                                                        Tallow fatty acid      1.7                                                    TiO.sub.2              0.5                                                    Moisture and minors    3.6                                                    Intimate mixture:                                                             Ditallowalkyldimethylammonium                                                                        5.2                                                    methyl sulfate                                                                Tallow alcohol         2.5                                                    Sorbitan monostearate  2.2                                                    ______________________________________                                    

An 11 × 11 inch bottom sheet, made of melt-blown polypropylene, isloaded with 32.7 grams of the detergent ingredients, in the form of anessentially anhydrous paste. The paste is thinly spread over the surfaceof one side of the substrate, leaving a clear perimeter edgeapproximately 1/2 inch wide. A second sheet of polypropylene is loadedwith the intimate mixture of the ditallowalkyldimethylammonium methylsulfate, tallow alcohol and sorbitan monostearate components. In formingthe intimate mixture, the components are melted, mixed together, andheld at a temperature of 140°-160° F. The mixture is loaded onto thistop sheet substrate by using a gravure printing process, in whichapproximately 4.4 grams of the mixture is imparted to the substrate, inrows of small dots. The two treated substrate sheets are then bondedtogether such that the spots of static control agent/dispersioninhibitor mixture are on an outside surface of the finished article, bybonding together the outer edges of both substrate sheets byheatsealing. This substrate article provides cleaning, fabric softeningand static control benefits when placed in an automatic washing machinewith a load of soiled fabrics during the washing cycle, and thensubsequently transferred to an automatic dryer and dried with thefabrics.

EXAMPLE IV

A substrate article of the present invention, containing the detergentand static control composition below, was made by the following method.

    ______________________________________                                        Component             % by weight                                             ______________________________________                                        Sodium C.sub.11.8 alkylbenzene                                                                      13.2                                                    sulfonate                                                                     C.sub.14-16 ethoxylated alkyl                                                                       6.9                                                     sulfate                                                                       Sodium silicate solids (2.Or)                                                                       13.2                                                    Tallow fatty acid     0.55                                                    Sodium tripolyphosphate                                                                             26.9                                                    Intimate mixture:                                                             Ditallowalkyldimethyl-                                                                              1.1                                                     ammonium methyl sulfate                                                       Sorbitan monostearate 2.7                                                     Tallow alcohol        1.3                                                     Moisture and minors   balance to 100                                          ______________________________________                                    

The intimate mixture of the ditallowalkyldimethylammonium methylsulfate, sorbitan monostearate and tallow alcohol components was made bya mixing and comelting process. A 2 inch wide strip of this mixture wasloaded on one edge of a Scott 8050 Industrial towel, using a gravureprinting process. The towel was then cut into sheets 8 × 103/4 inch. Onesheet, used as the bottom substrate sheet, was loaded with about 70grams of a mixture of the detergent active components, spread in a thinlayer on the side opposite the side containing the intimate mixturestrip, leaving a clean perimeter edge all around the substrate sheet. Asecond sheet of the towel was then laid on top of the sheet containingthe detergent active, such that the intimate mixture strip on the topsheet was on the outer side of the finished product. The two substratesheets were placed such that both strips of the intimate mixture wouldbe on the outside of the finished article, and the two strips would beon opposite ends of the article. The two sheets were bonded together bysewing around the clean outer perimeter edge. The final substratearticle carried about 3.6 grams of the intimate mixture component. Thissubstrate article was found to give particularly beneficial cleaning,softening, and static control performance when used sequentially in anautomatic washing machine and automatic clothes dryer in the launderingprocess.

EXAMPLE V

Cleaning and conditioning substrate articles were made by coating about35 grams of a detergent composition, having the formulation given below,on one side of an 8 × 11 inch sheet of a Scott Industrial Towel, made ofwood pulp, rayon and latex binder. An identical sheet of the same typeof towel was placed on top of the coated sheet, and the edges of the twosheets were sewn together, so as to completely enclose the detergentcomposition between the two substrate sheets.

    ______________________________________                                        Component               % by weight                                           ______________________________________                                        Condensation product of                                                       C.sub.14-15 alcohol with average 7                                            moles of ethylene oxide per                                                   mole of alcohol (Neodol 45-7)                                                                         28.3                                                  Triethanolamine         6.6                                                   Magnesium C.sub.11.8 linear                                                   alkylbenzene sulfonate  59.0                                                  Tallow fatty acid       1.9                                                   Moisture and minors     4.2                                                   ______________________________________                                    

A fabric softening and static control mixture was formulated bycomelting and mixing ditallowalkyldimethylammonium chloride and tallowalcohol, in a ratio of about 3:1, at a temperature of about 190°-200° F.

Three different types of articles were formulated using the intimatemixture and the substrate articles formulated above. Each of thearticles contained 2.5 grams of the quaternary ammonium/dispersioninhibitor intimate mixture. Article A was made by placing 1 to 11/4 inchwide strips of the intimate mixture along the 8 inch edges of thesubstrate articles, using a gravure printing process. The strips coveredabout 40 sq. inches of the substrate surface, did not penetrate into thesubstrate material and were less than 1/32 inch in height. Article B wasmade by placing 24 spots of the intimate mixture on the substratesurface, such that they covered about 4 sq. inches of the substratesurface. The spots penetrated into the substrate material, and each hada diameter of about 3/8 inch and a thickness of about 1/32 to 1/16 inchabove the substrate surface. Article C was formulated by hand coatingthe intimate mixture in 1 to 11/4 inch wide strips along the 8 inchsubstrate edges such that about 40 sq. inches of the substrate surfacewas covered by the mixture. There was some penetration of the mixtureinto the substrate material, and the strips had a height of less than1/32 inch.

Each of the substrate articles was then used to launder fabrics, underidentical conditions, using a Kenmore Automatic Washing Machine. Foreach run a standard 51/2 lb. load of clothing, containing synthetic,natural, and blended fiber garments, was washed in a regular agitationcycle, in 100° F wash water which had a hardness of 7 grains of mixedcalcium and magnesium per gallon of water. Each load of clothing,together with its substrate article, was then transferred to a KenmoreElectric Dryer and was dried for 50 minutes at a maximum temperature ofabout 155° F. The test procedures were carried out at a relativehumidity of about 30-35%.

The dried clothes were then inserted in a Faraday Cage Voltage SensingBasket and the voltage level change was measured as each item ofclothing was removed from the Faraday Cage, yielding the total voltagecharge per wash load. The total voltage charge was then divided by theamount of fabric surface area in the wash load to calculate the voltageper area. In addition, the number of static clings taking place asindividual clothing articles were removed from the dryer was recordedfor each wash load. Lower voltage per area and static cling figuresdenote better static control performance by the composition utilized inthe washing/drying process. The results for each of the articles issummarized in the table below.

    ______________________________________                                        Article   Voltage/yd..sup.2                                                                            #fabric clings                                       ______________________________________                                        A         2.1            2                                                    B         0.4            0                                                    C         1.4            0                                                    ______________________________________                                    

The data indicate that improved static control results are obtainedwhere laundry/fabric conditioning substrate articles are formulated suchthat the fabric conditioner/dispersion inhibitor mixture penetrates intothe substrate material and has a height above the substrate material offrom 1/32 to about 1/2 inch.

Substantially similar static control results are obtained where ArticleB is formulated such that the quaternary ammonium/dispersion inhibitorspots are about 1/8 inch or about 1/4 inch in height, and also where thespots cover about 3 sq. inches or about 6 sq. inches of the substratesurface area. Comparable results are also obtained where the ratio byweight of ditallowalkyldimethylammonium chloride to tallow alcohol isabout 1:1.

Substantially similar results are obtained where the detergentcomposition carried by the substrate article includes anionicsurfactants, particularly sodium, calcium, or magnesium-neutralizedanionic surfactants, such as C₁₀₋₁₆ branched chain alkylbenzenesulfonates, C₁₀₋₁₆ alkyl sulfates, or C₁₀₋₁₆ alkyl ether sulfates.

Comparable results are also obtained where the detergent compositioncontains a nonionic surfactant such as a secondary C₁₁₋₁₅ alcoholcondensed with 9 moles of ethylene oxide (Tergitol 15-S-9), thecondensation product of C₁₂₋₁₃ alcohol with an average of 5 moles ofethylene oxide, wherein the mono- and unethoxylated fractions arestripped away (Neodol 23-3T), or the condensation product of nonylphenolwith 9 moles of ethylene oxide (Igepal CO-630).

Similar results are obtained where the detergent composition carried bythe substrate articles contains a builder component such as awater-insoluble aluminosilicate builder, e.g., hydrated sodium Zeolite Awith an average particle size of 1-10 microns, sodium pyrophosphate,sodium carbonate, or sodium 2-oxy-1,1,3-propane tricarboxylate.

Similar results are also obtained where the quaternary ammoniumcomponent used in the substrate article is ditallowalkyldimethylammoniummethyl sulfate, dicetyldimethylammonium chloride,didodecyldimethylammonium chloride, ditallowalkyldimethylammoniumbromide, dioleoyldimethylammonium hydroxide,ditallowalkyldipropylammonium chloride, ditallowalkyldibutylammoniumfluoride, or cetyldecylmethylethylammonium chloride.

Comparable results are also obtained where the dispersion inhibitor usedin the substrate article is replaced by myristyl alcohol, cetyl alcohol,stearyl alcohol, lauric acid, myristic acid, palmitic acid, stearicacid, sorbitan trilaurate, sorbitan trimyristate, sorbitan tripalmitate,or sorbitan tetrastearate.

What is claimed is:
 1. A laundry article, providing cleaning and fabricconditioning benefits, for use in both the washer and the dryer,consisting essentially of a water-insoluble substrate, carrying:(a) aneffective amount of a detergent composition comprising from about 5 to95% of a water-soluble surface-active agent; and (b) an effective amountof an intimate mixture, having a maximum solubility in water of 50 ppmat 25° C, and a softening point of from 100° to 200° F, consistingessentially of(i) from about 10 to 90% by weight of quaternary ammoniumfabric-conditioning compounds having the formula [R₁ R₂ R₃ R₄ N]⁺ Y⁻,wherein one or two of the R₁, R₂, R₃, or R₄ groups is an organic radicalcontaining a group selected from a C₁₂ to C₂₂ aliphatic radical, or analkyl phenyl or alkyl benzyl radical having 10 to 16 carbon atoms in thealkyl chain, the remaining group or groups being selected from C₁ to C₄alkyl, C₂ to C₄ hydroxy alkyl, and cyclic structures in which thenitrogen atom forms part of the ring, Y constitutes an anionic radicalselected from the group consisting of hydroxide, halide, sulfate, methylsulfate, and phosphate ions; and (ii) from about 10 to 90% by weight ofa dispersion inhibitor, being a solid organic material having a maximumsolubility in water of 50 ppm at 25° C and a softening point in therange of 100° to 200° F, said material being selected from the groupconsisting of paraffinic waxes, cyclic and acyclic mono- and polyhydricalcohols, substituted and unsubstituted aliphatic carboxylic acids,esters of cyclic and acyclic mono- and polyhydric alcohols and acids,condensates of C₂ to C₄ alkylene oxide with any of the foregoing typesof materials whether or not said materials themselves meet the abovesolubility and softening point limits, and mixtures thereof.
 2. Anarticle according to claim 1 wherein the substrate is made of aflexible, water-insoluble wet-strength paper, woven cloth or nonwovencloth.
 3. An article according to claim 2 wherein the surface-activeagent is selected from the group consisting of anionic surfactants,nonionic surfactants, zwitterionic surfactants, and mixtures thereof. 4.An article according to claim 3 wherein the surface-active agent ispresent, in the detergent composition, in an amount from about 15 to 90%by weight.
 5. An article according to claim 4 wherein the substratecarries from about 1 to 20 grams of the intimate mixture of quaternaryammonium fabric conditioning compound and dispersion inhibitor.
 6. Anarticle according to claim 5 wherein the substrate carries from about 3to 120 grams of the detergent composition.
 7. An article according toclaim 6 wherein the weight ratio of quaternary ammonium compound todispersion inhibitor is in the range of from about 4:1 to 1:4.
 8. Anarticle according to claim 7 wherein the weight ratio of quaternaryammonium compound to dispersion inhibitor is in the range of from about3:1 to 1:3.
 9. An article according to claim 8 wherein the intimatemixture is formed from a comelt of the quaternary ammonium compound andthe dispersion inhibitor.
 10. An article according to claim 9 whereinthe dispersion inhibitor has a softening point in the range of fromabout 150° to 175° F.
 11. An article according to claim 9 wherein theintimate mixture of quaternary ammonium compound and dispersioninhibitor is carried by the substrate in areas having an averagediameter of greater than about 500 microns.
 12. An article according toclaim 9 wherein the quaternary ammonium compound is selected from thegroup consisting of ditallowalkyldimethylammonium chloride,ditallowalkyldimethylammonium methyl sulfate, anddioctadecyldimethylammonium chloride.
 13. An article according to claim12 wherein the dispersion inhibitor is selected from the groupconsisting of tallow alcohol, and C₁₀ to C₂₂ alkyl sorbitan esters, andmixtures thereof.
 14. An article according to claim 13 wherein thedispersion inhibitor is a mixture of C₁₀ to C₂₂ alkyl sorbitan esters,the major component of which is one or more esters selected from thegroup consisting of sorbitan trilaurate, sorbitan trimyristate, sorbitantripalmitate, sorbitan tetralaurate, sorbitan tetramyristate, sorbitantetrapalmitate, sorbitan tetrastearate, and mixtures thereof.
 15. Anarticle according to claim 13 wherein the dispersion inhibitor is amixture of sorbitan monostearate and tallow alcohol.
 16. An articleaccording to claim 13 wherein the substrate carries from about 2 to 8grams of the intimate mixture.
 17. An article according to claim 16wherein the detergent composition contains from about 1 to 60% of adetergent builder.
 18. An article according to claim 17 wherein theintimate mixture consists essentially of ditallowalkyldimethylammoniumchloride and tallow alcohol in a ratio of about 1:1 by weight.
 19. Amethod of laundering and conditioning fabrics comprising the stepsof:(a) agitating said fabrics in an aqueous laundry solution to whichhas been added a substrate composition carrying an effective amount of adetergent composition, such that said detergent composition is dissolvedin the laundry solution, and a fabric conditioning agent, such that saidconditioning agent is not substantially dissolved in the laundrysolution; and (b) tumbling said fabrics, under heat, in a laundry dryertogether with said substrate composition such that said conditioningagent is transferred to said fabrics while they are being dried.
 20. Amethod of providing cleaning, fabric softening and static controlbenefits to fabrics, comprising the steps of:(A) agitating said fabricsin an aqueous laundry solution to which has been added a water-insolublesubstrate detergent composition consisting essentially of awater-insoluble substrate, carrying(a) an effective amount of adetergent composition comprising from about 5 to 95% of a water-solublesurface-active agent; and (b) an effective amount of an intimatemixture, having a maximum solubility of 50 ppm at 25° C, and a softeningpoint of from 100° to 200° F, consisting essentially of:(i) from about10 to 90% by weight of a quaternary ammonium fabric conditioningcompound having the formula [R₁ R₂ R₃ R₄ N]⁺ Y⁻, wherein one or two ofthe R₁, R₂, R₃, or R₄ groups is an organic radical containing a groupselected from a C₁₂ to C₂₂ aliphatic radical, or an alkyl phenyl oralkyl benzyl radical having 10 to 16 carbon atoms in the alkyl chain,the remaining group or groups being selected from C₁ to C₄ alkyl, C₂ toC₄ hydroxy alkyl, and cyclic structures in which the nitrogen atomsforms at least part of the ring, and Y constitutes an anionic radicalselected from the group consisting of hydroxide, halide, sulfate, methylsulfate, and phosphate ions; and (ii) from about 10 to 90% by weight ofa dispersion inhibitor, being a solid organic material having a maximumsolubility of 50 ppm at 25° C and a softening point in the range of 100°to 200° F, said material being selected from the group consisting ofparaffinic waxes, cyclic and acyclic mono- and polyhydric alcohols,substituted and unsubstituted aliphatic carboxylic acids, esters ofcyclic and acyclic mono- and polyhydric alcohols and acids, condensatesof C₂ to C₄ alkylene oxide with any of the foregoing types of materialswhether or not said materials themselves meet the above solubility andsoftening point limits, and mixtures thereof; and (B) tumbling saidfabrics, under heat, in a laundry dryer together with said substratecomposition.
 21. A method according to claim 20 wherein the substrate ismade of a flexible, water-insoluble wet-strength paper, woven cloth ornonwoven cloth.
 22. A method according to claim 21 wherein thesurface-active agent is selected from the group consisting of anionicsurfactants, nonionic surfactants, zwitterionic surfactants, andmixtures thereof.
 23. A method according to claim 22 wherein thesubstrate carries from about 1 to 20 grams of the intimate mixture. 24.A method according to claim 23 wherein the intimate mixture ofquaternary ammonium compound and dispersion inhibitor is carried by thesubstrate in areas having an average diameter of greater than about 500microns.
 25. A method according to claim 23 wherein the weight ratio ofquaternary ammonium compound to dispersion inhibitor lies in the rangeof from about 4:1 to 1:4.
 26. A method according to claim 25 wherein thequaternary ammonium compound is selected from the group consisting ofditallowalkyldimethylammonium chloride, ditallowalkyldimethylammoniummethyl sulfate, and dioctadecyldimethylammonium chloride.
 27. A methodaccording to claim 26 wherein the dispersion inhibitor is selected fromthe group consisting of tallow alcohol, C₁₀ to C₂₂ alkyl sorbitanesters, and mixtures thereof.
 28. A method according to claim 27 whereinthe dispersion inhibitor is a mixture of sorbitan monostearate andtallow alcohol.
 29. A method according to claim 28 wherein the substratecarries from about 3 to 120 grams of the detergent composition.